CN104788617A

CN104788617A - Method for reducing color number of cyclopentadiene petroleum resin

Info

Publication number: CN104788617A
Application number: CN201510164615.2A
Authority: CN
Inventors: 沈阳; 王占新
Original assignee: Individual
Current assignee: Individual
Priority date: 2015-04-09
Filing date: 2015-04-09
Publication date: 2015-07-22
Anticipated expiration: 2035-04-09
Also published as: CN104788617B

Abstract

The invention discloses a method for reducing the color number of cyclopentadiene petroleum resin. A C5 olefin fraction is taken as a raw material and added to a high-pressure reactor together with a solvent and a catalyst, inert gas in fed to remove air, proper inert gas pressure is guaranteed, and the cyclopentadiene petroleum resin is prepared at a proper reaction temperature for a proper reaction time. On the premise that the performance of high-end products is met, the process is simple, the investment is low, the catalyst is not required to be removed, wastewater containing fluoride and the like cannot be produced, and the method has the characteristics of environment friendliness, high efficiency and good benefit.

Description

A kind of method reducing cyclopentadiene petroleum resin look number

Technical field

The invention belongs to petroleum resin synthesis field, be specifically related to a kind of method reducing cyclopentadiene petroleum resin look number.

Background technology

Cyclopentadiene petroleum resin synthesis mainly contains 2 kinds, and one is low temperature process, and temperature is generally no more than 80 DEG C, adopt aluminum chloride, boron trifluoride etc. are as catalyzer, and advantage is that product look is number low, the product of less than No. 5 can be produced, can meet high-end market demand, shortcoming is that technical process is complicated, and catalyzer uses inconvenience, easy blocking pipe, expensive, particularly removing of catalyzer can produce a large amount of waste water, and environmental protection pressure is large; Another kind is pyroprocess, and temperature, generally at 200-300 DEG C, adopts or do not adopt catalyzer, and advantage is that flow process is simple, and environmental protection pressure is little, and shortcoming generally to produce the product of more than No. 10, and can not meet high-end market demand, benefit is low.

Summary of the invention

Goal of the invention: the object of the invention is for the deficiencies in the prior art, provides a kind of method reducing cyclopentadiene petroleum resin look number.

Technical scheme: in order to reach foregoing invention object, the present invention has specifically come like this: a kind of method reducing cyclopentadiene petroleum resin look number, with C ₅olefin fraction is raw material, and it is added high-pressure reactor with solvent together with catalyzer, passes into rare gas element excluding air, and ensures suitable inert gas pressure, under suitable temperature of reaction, carries out the suitable reaction times, obtained cyclopentadiene petroleum resin.

Wherein, described solvent is dimethylbenzene, ethylbenzene or hexane.

Wherein, described C ₅in olefin fraction, cycle pentadiene dimer enriched material weight is 84 ~ 86%.

Wherein, described catalyzer by initiator, antiaging agent, thermo-stabilizer forms, and initiator is selected from one in Diisopropyl azodicarboxylate, dicumyl peroxide or all; Antiaging agent is selected from 2,5-dimethyl-2, two (tert-butyl peroxide) hexane of 5-, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three [2,4-di-tert-butyl-phenyl] phosphorous acid ester, one or more in β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid; Thermo-stabilizer is selected from the one or all in calcium stearate, Zinic stearas; Preferably, described catalyzer is by Diisopropyl azodicarboxylate, dicumyl peroxide, 2,5-dimethyl-2, two (tert-butyl peroxide) hexane of 5-, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three [2,4-di-tert-butyl-phenyl] phosphorous acid ester, β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, calcium stearate, Zinic stearas in mass ratio 1:2:1:0.5:1:0.5:0.3:0.2 mix, catalyst charge is 0.1 ~ 0.8% of C5 olefin fraction quality.

Catalyzer forms 1 ~ 5:1 ~ 4:0.2 ~ 1 in mass ratio by initiator, antiaging agent and thermo-stabilizer and forms; Initiator in catalyzer can ensure that reactant can start reaction at lesser temps, and favors low temperature has lower look number in product, can reduce the reaction times simultaneously, enhance productivity; Antiaging agent can ensure that reactant does not react with the compound of oxygen and oxygen, is conducive to the low look number of product, and reaction terminate after need not be separated, ensure that product is in storage, can not color burn during use; Thermo-stabilizer can to ensure in reaction process in (150 ~ 300 DEG C) and use procedure (generally at 180 ~ 220 DEG C), reactant and product can not produce thermo-cracking and generate and be similar to colloid, the dark macromole goods and materials such as bituminous matter, thus do not affect product performance and use.

Wherein, described rare gas element is selected from nitrogen, argon gas or helium, and control pressure is in 0.5 ~ 1.5MPa.

Wherein, described temperature of reaction is 150 ~ 300 DEG C.

Wherein, the described reaction times is 2 ~ 12h.

Wherein, described solvent and C ₅the mass ratio that adds of olefin fraction is 0.7 ~ 1.5:10.

Beneficial effect: the present invention is under the prerequisite meeting high-end product performance, and flow process is simple, less investment, and catalyzer does not need to remove, and can not produce fluorine-containing waste water of Denging, have environmental protection, efficiently, profitable feature.

Embodiment

Embodiment 1

1, get 3g composite catalyst, the solvent of 80g, the C5 of 1000g add reaction unit, open and stir 20min; Wherein catalyzer is by Diisopropyl azodicarboxylate, dicumyl peroxide, 2,5-dimethyl-2, two (tert-butyl peroxide) hexane of 5-, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three [2,4-di-tert-butyl-phenyl] phosphorous acid ester, β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid, calcium stearate, Zinic stearas in mass ratio 1:2:1:0.5:1:0.5:0.3:0.2 mix.

2, keep stirring, logical rare gas element, 10min, confined reaction device, keeps the inert gas pressure of 0.1MPa.

3, at 180 DEG C, react 10h, be cooled to 60 DEG C.

4, distilled by reaction mass, steaming solvent and oligopolymer, is product at the bottom of still.

5, analysed preparation data, are mainly look number and softening temperature.

Embodiment 2

With embodiment 1, difference is, temperature of reaction 200 DEG C is according in table 1.

Embodiment 3

With embodiment 1, difference is, temperature of reaction 220 DEG C is according in table 1.

Embodiment 4

With embodiment 1, difference is, temperature of reaction 240 DEG C is according in table 1.

Embodiment 5

With embodiment 1, difference is, temperature of reaction 260 DEG C is according in table 1.

Embodiment 6

With embodiment 1, difference is, temperature of reaction 280 DEG C.Data are in table 1.

Embodiment 7

With embodiment 4, difference is, catalyst charge is 0.1%, and data are in table 1.

Embodiment 8

With embodiment 4, difference is, catalyst charge is 0.2%, and data are in table 1.

Embodiment 9

With embodiment 4, difference is, catalyst charge is 0.4%, and data are in table 1.

Embodiment 10

With embodiment 4, difference is, catalyst charge is 0.5%, and data are in table 1.

Embodiment 11

With embodiment 4, difference is, catalyst charge is 0.6%, and data are in table 1.

Embodiment 12

With embodiment 4, difference is, catalyst charge is 0.7%, and data are in table 1.

Embodiment 13

With embodiment 4, difference is, the reaction times is 5h, and data are in table 1.

Embodiment 14

With embodiment 4, difference is, the reaction times is 6h, and data are in table 1.

Embodiment 15

With embodiment 4, difference is, the reaction times is 7h, and data are in table 1.

Embodiment 16

With embodiment 4, difference is, the reaction times is 8h, and data are in table 1.

Embodiment 17

With embodiment 4, difference is, the reaction times is 9h, and data are in table 1.

Embodiment 18

With embodiment 4, difference is, the reaction times is 11h, and data are in table 1.

Embodiment 19

With embodiment 4, difference is, the reaction times is 12h, and data are in table 1.

Embodiment 20

With embodiment 17, difference is, solvent and reactant mass ratio are 0, and data are in table 1.

Embodiment 21

With embodiment 17, difference is, solvent and reactant mass ratio are 0.05, and data are in table 1.

Embodiment 22

With embodiment 17, difference is, solvent and reactant mass ratio are 0.1, and data are in table 1.

Embodiment 23

With embodiment 17, difference is, solvent and reactant mass ratio are 0.15, and data are in table 1.

Embodiment 24

With embodiment 17, difference is, solvent and reactant mass ratio are 0.2, and data are in table 1.

Embodiment 25

Except catalyzer, with embodiment 4; Catalyzer is by Diisopropyl azodicarboxylate, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, and calcium stearate, Zinic stearas in mass ratio 1:2:1 mix.

Embodiment 26

Except catalyzer, with embodiment 4; Catalyzer by dicumyl peroxide, two (tert-butyl peroxide) hexanes of 2,5-dimethyl-2,5-, three [2,4-di-tert-butyl-phenyl] phosphorous acid ester, Zinic stearas in mass ratio 1:2:1:0.5 mix.

Embodiment 27

Except catalyzer, with embodiment 4; Catalyzer is by Diisopropyl azodicarboxylate, dicumyl peroxide, three [2,4-di-tert-butyl-phenyl] phosphorous acid ester, β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid, calcium stearate, Zinic stearas in mass ratio 1:2:1:1:0.5:0.5 mix.

Data as can be seen from table 1, cyclopentadiene petroleum resin prepared according to the methods of the invention, compared with existing 2 kinds of preparation methods, have the two advantage concurrently and without the two shortcoming, product look is number low, and softening temperature is adjustable in acceptability limit, does not use catalyzer environment being had to larger pollution simultaneously, the catalyzer used need not remove from product, and is conducive to the performance of product in follow-up use.

Table 1

Claims

1. reduce a method for cyclopentadiene petroleum resin look number, it is characterized in that, C ₅olefin fraction is raw material, and it is added high-pressure reactor with solvent together with catalyzer, passes into rare gas element excluding air, and ensures suitable inert gas pressure, under suitable temperature of reaction, carries out the suitable reaction times, obtained cyclopentadiene petroleum resin.

2. the method for reduction cyclopentadiene petroleum resin look according to claim 1 number, it is characterized in that, described solvent is dimethylbenzene, ethylbenzene or hexane.

3. the method for reduction cyclopentadiene petroleum resin look according to claim 1 number, is characterized in that, described C ₅in olefin fraction, cycle pentadiene dimer enriched material weight is 84 ~ 86%.

4. the method for reduction cyclopentadiene petroleum resin look according to claim 1 number, it is characterized in that, described catalyzer is by initiator, antiaging agent, thermo-stabilizer 1 ~ 5:1 in mass ratio ~ 4:0.2 ~ 1 forms, and initiator is selected from the one or all in Diisopropyl azodicarboxylate, dicumyl peroxide; Antiaging agent is selected from 2,5-dimethyl-2, two (tert-butyl peroxide) hexane of 5-, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three [2.4-di-tert-butyl-phenyl] phosphorous acid ester, one or more in β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid; Thermo-stabilizer is selected from the one or all in calcium stearate, Zinic stearas.

5. the method for reduction cyclopentadiene petroleum resin look according to claim 1 or 4 number, it is characterized in that, described catalyzer is by Diisopropyl azodicarboxylate, dicumyl peroxide, 2, 5-dimethyl-2, two (tert-butyl peroxide) hexane of 5-, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three [2, 4-di-tert-butyl-phenyl] phosphorous acid ester, β-(3, 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, calcium stearate, Zinic stearas in mass ratio 1:2:1:0.5:1:0.5:0.3:0.2 mixes, catalyst charge is C ₅0.1 ~ 0.8% of olefin fraction quality.

6. the method for reduction cyclopentadiene petroleum resin look according to claim 1 number, it is characterized in that, described rare gas element is selected from nitrogen, argon gas or helium, and control pressure is in 0.5 ~ 1.5MPa.

7. the method for reduction cyclopentadiene petroleum resin look according to claim 1 number, it is characterized in that, described temperature of reaction is 150 ~ 300 DEG C.

8. the method for reduction cyclopentadiene petroleum resin look according to claim 1 number, it is characterized in that, the described reaction times is 2 ~ 12h.

9. the method for reduction cyclopentadiene petroleum resin look according to claim 1 and 2 number, is characterized in that, described solvent and C ₅the mass ratio that adds of olefin fraction is 0.7 ~ 1.5:10.